Ditolylmethane azo-dyestuffs and process of making same



'Paten tecl Oct. 30, 1928.

UNITED STATES 1,689,740 PATENT OFFICE.

CARL MET'ILER, or BASEL, SWITZERLAND, AssIGNoRTo THE FIRM J. R. GEI Y- A. o...

e or BAsEL, SWITZERLAND.

DITOLYLMETHANE Azo-nYEs Urrs Ann rnoc'nss or MAKINGI' SAME.

No Drawing. Original application filed January 14, 1927, Serial N 161,240, and in Germany January 28, 1926. Divided and this application filed November 1927. Serial No. 235,759.

This application is divisional of the application Ser. No. 1G1,2 l(),tiled January- 14,

' When aniline reacts with chloromethyl-o r- 5 tho-cresotinic acid, there is obtained in good yield aniline-n'iethylene-ortho cresotinic acid in accordance with the following equation coon . CH3 I OHTON lIl CH3 Like derivatives of diphenylimethane are obtained when there 18 used instead of anil ne another amine of the benzene or naphthalene coon cresotinic acid another chloromethyl deriva-' tlve of an ortho-hydroxycarboxyl1c acid.

Hitherto these compounds have not found application in the manufacture of dyestufli's.

By the present invention a new series of niordant dyeing also-dyestuffs is obtained by diazotizing a derivative of a'ditolyhnethane containing in one nucleus an amino-group an orthohydroxy-carboxylic acid group, and

coupling the product with any azo-dyestutt component.

The dyestufis thus made are valuable because when a chromium salt'is added they 3 yield in cotton printing red and violet tints which are as vivid as those which hitherto An analogous red tint of like properties is obtained when 1-napthol-3 S-disulphoni c acid series, and instead of chloroniethyl orthocapable of being diazotized and in the other sodium carbonate.

That the ditolyln'iethanes in question could be used for a smooth production of azo-dyestuilis was not to be expected; for nitrous acid frequently acts to decompose such diarylinethanes having two auxochronie groups in paraor ortho-position to the methane resi due, or to oxidize them atthe methane group (see German patent specification No. 245,-

769). The production'of such pure tintswith these mordant dyestufi's was'not to be expected. i r The following example illustrates the invention:

20 kilos of chloromethyl-ortho-cresotinic acid see German patent specification No. 236,046) are boiled with 200 litres of water and 21,4: kilos of toluidine for 16 hours in a reflux apparatus. \Vhen the mass has cooled it is made alkaline with sodium carbonate and the unaltered toluidine is distilled in steam. By addition of hydrochloric acid the orth-o toluidine methylene ortho cresotinic acid is precipitated. When dry it is a colorless powder, which is insoluble in water but passes into solution on addition of sodium carbonate. A quantity of the ortho-toluidineniethylene-ortho-cresotinic acid corresponding with 6.9 kilos of sodium nitrite is diazotized in cold hydrochloric acid and'coupled with the calculated quantity of l-naphtol- 3: G-disulphonic acid in solution alkaline with After stirring for 24. hours the whole is warniedand the dyestuff salted out. When dry it is a brown-red powder, easily soluble in water to ayellow-red solution and in concentrated sulphuric acid to a yellowish red solution. When printed on cotton with a chromiuin'salt a clear vivid red is provided which is fast to boiling soap, sodi-.

um carbonate and chlorine. On wool. it yields from an acetic acid bath yellowish-red tints. The product obtained accorliling to this example may have the'following formula:

soin soin the product constitutes in form of its sodium salt a red powder easily soluble in water and is used as second component. In both cases, concentrated sulphuric acid with a red color,

kind may be used whereby dyestuffs of very different tints and fastness areobtained. I

What I claim is:

Y 1. A process for the manufacture of mordant dyeing azo-dyestufls,

consisting-1 in diazotizing a ditolylmethane derivative which contnaiins" in one nucleus an amino-group and in the other an orthohydroxy-carboxylic acid group, and coupling with an axo-dyestufi' component.

P duc o u h an- 2. A process for the manufacture of mordant dyeing azo-dyestufis, consisting in diazotizing ortho-toluidine-methylene-orthocresotinic acid and coupling with an azo-jdyetu c mpone r 3. Aprocess for-thexnanufacture of inor dantd 'ein aZo-d estuffs consistin in diazotizing cresotinic acid and coupling with l-napthol- 3 =6- is i ph-Qnic mid o t al a n almon .4. As anew article of manufacture the hereinbeiore described mordant dyeing dyestufi obtained by diazotizing ortho-tolu-idinemethylene-ortliocresotinio acid and coupling with 1-napthol-3 6-disulphonic acid and constituting in form o f its sodium salt a red powortho-toluidineanethylene-orthoder easily soluble in water and concentrated sulphuric acid with a red color andyielding red tints on. wool from any acetio acid bath and when printed. on cotton with a chromium salt. 1

In witness whereof I have hereunto; signed my name this 11th day of November, 1927. e V CARL MET'ILER; 

